JPH09132767A - Composition for surface treatment for gas barrier and resin molding of surface treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having transparency and flexibility not to damage physical properties of a material to be treated and extremely slight humidity and temperature dependence of gas barrier properties, comprising a reaction product of a specific silane compound, etc., and a solvent. SOLUTION: This composition for surface treatment comprises a reaction product of (A) a silane compound of formula I (A<1> is an alkylene; R<1> is H, a lower alkyl or a group of formula II; R<2> is H or a lower alkyl; R<3> is a lower alkyl, an aryl or an unsaturated aliphatic residue; R<4> is H, a lower alkyl or an acyl; (w) is 0, 1 or 2; (z) is 1-3), (B) a compound which contains an aromatic ring or a hydrogenated aromatic ring and two more functional groups in the molecule, having reactivity with the amino group and/or an Si(OR<4> ) group in the component A and (C) an organometallic compound composed of (i) an organometallic compound of formula III or of a mixture of the component (i) and (ii) an organic silane compound of formula IV (M is a metal element except Si; R<7> and R<9> are each as shown for R<3> ; R<8> and R<10> are each as shown for R<4> ; (m) is 0 or a positive number; (n) is >=1, etc.) and (D) a solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas-barrier surface treatment composition which is excellent in transparency and flexibility and can form a film having extremely low gas-barrier humidity and temperature dependence. The present invention relates to a processed resin molded article.

[0002]

2. Description of the Related Art There is an increasing demand for gas barrier materials having extremely low permeability of gases such as oxygen, nitrogen, carbon dioxide, water vapor and the like in the field of packaging materials and the like. In order to impart a gas barrier property to a molded material such as a plastic film or sheet, a molded article is formed from a gas-impermeable material such as an ethylene-vinyl alcohol copolymer, a vinylidene chloride-based copolymer, or polymethaxylylene adipamide. There are known methods of forming, laminating or coating these gas impermeable materials with other materials, laminating aluminum foil with film materials, and vapor-depositing metal oxides.

However, among the gas impermeable materials, ethylene-vinyl alcohol copolymer and polymetaxylylene adipamide have a large hygroscopic property, and there is a problem that the gas barrier property is significantly lowered due to the moisture absorption. Since the vinylidene chloride-based copolymer contains a chlorine atom, it may cause pollution. Also, with the aluminum foil laminated film, the packaged contents cannot be seen from the outside,
Since the metal vapor-deposited film of (1) deteriorates flexibility and the like, there is a problem that cracks easily occur in the vapor-deposited layer during packaging, which causes deterioration of gas barrier properties.

[0004] In order to solve these problems, studies have been made on surface treatment of plastic films using polysiloxane having a dense molecular structure and having excellent weather resistance, hardness and chemical resistance. . However, tetraalkoxysilane used as a raw material of polysiloxane has four hydrolysis-condensation reaction points and therefore has a large volume shrinkage at the time of condensation, and it has been difficult to obtain a coating film free of cracks and pinholes.

[0005] Therefore, it has been proposed to suppress the occurrence of cracks and pinholes by conducting hydrolysis-condensation condensation of an alkyltrialkoxysilane having only three hydrolysis-condensation reaction points alone or with tetraalkoxysilane. However, since alkyltrialkoxysilane has low reactivity, the monomer remaining without condensation by using alkyltrialkoxysilane alone increases, and when used in combination with tetraalkoxysilane, it is not possible to perform a uniform co-hydrolytic condensation. That was the current situation. Furthermore, since these silane-based surface treatment compositions have no affinity for plastic film materials and have poor wettability, there is also a problem that film forming properties are poor.

Japanese Patent Application Laid-Open No. 2-286331 discloses that
It has been shown that the alkoxysilane is hydrolyzed and condensed and coated on a plastic film. However, in this method, since only the alkoxysilane component is coated on the film, the flexibility of the film is significantly impaired.

In view of the above, for example, Japanese Patent Application Laid-Open No. 1-2785
No. 74 discloses that cracking of a surface treatment film is suppressed by combining an alkoxysilane hydrolyzate such as tetraalkoxysilane with a reactive urethane resin. However, since the reactive urethane resin reacts with alcohols used as a solvent, the alkoxysilane hydrolyzate and the reactive urethane resin are not sufficiently complexed to cause phase separation, and the coating may become opaque. there were.

[0008]

In consideration of the above-mentioned problems, the present inventors have transparency, flexibility so as not to impair the physical properties of the object to be treated, and gas and humidity dependence on humidity and temperature. It is a second object of the present invention to provide a gas barrier surface treatment composition having extremely low property, and to provide a resin molded article surface-treated with the composition.

[0009]

According to the present invention, a composition for surface treatment comprises (1) a silane compound (A) represented by the following general formula (I):

[0010]

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Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or

[0012]

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(In the formula, A ² represents a direct bond or an alkylene group, and R ⁵ and R ⁶ represent a hydrogen atom or a lower alkyl group)
R ² represents a hydrogen atom or a lower alkyl group, R ³ represents the same or different lower alkyl group, aryl group or unsaturated aliphatic residue, and R ⁴ represents a hydrogen atom, a lower alkyl group or an acyl group. (However, R ¹ , R ² , R ⁵ , R
⁶ is at least one hydrogen atom), w is 0,
Any one of 1, 2 and z represents an integer of 1 to 3 (w + z = 3)]

An amino group and / or S in the silane compound (A) having an aromatic ring or a hydrogenated ring thereof.
a compound (B) having two or more functional groups having reactivity with an i (OR ⁴ ) group in the molecule; and an organometallic compound (C ₁ ) R ⁷ _mM M (OR _{^{8) n ... (II) (}} M in the formula is a metal element excluding Si, R ⁷ may be the same or different, represent a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue, R ⁸ May be the same or different and represent a hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, n is an integer of 1 or more, and m + n matches the valence of the metal element M), Alternatively, the organometallic compound (C ₁ ) is represented by the following general formula (I
Organic silane compound represented by II) (C ₂₎ a mixture organometallic compound which is a (C ₁ + C ₂₎ [Note that combined both organometallic compound (C ₁₎ and organometallic compound (C ₁ + C ₂₎ R ⁹ _o Si (OR ¹⁰ ) _p ... (III) (wherein R ⁹ may be the same or different and represents a hydrogen atom, a lower alkyl group, an aryl group or Represents an unsaturated aliphatic residue, R ¹⁰ may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group, o is 0 or a positive integer, p is an integer of 1 or more, and o + p is S
reaction product with the valence of i) (ABC),
(2) a reaction product (PABC) in which the silane compound (A) is (co) hydrolyzed and condensed before or after the reaction between the organometallic compound (C) and the organic compound (B);
The present invention relates to a gas barrier surface treatment composition characterized by comprising one or more reactive compounds selected from the group consisting of (1) and (2) and a solvent (D). Further, a surface-treated resin molded product obtained by treating at least one surface of the resin molded product surface with the composition for surface treatment is also included in the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION A silane compound (A) represented by the following general formula (I) used in the present invention.

[0016]

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(Where A ¹ , R ¹ , R ² , R ³ , R ⁴ , w,
The meaning of z is the same as described above) is not particularly limited as long as it is a silane compound having an amino group and a hydrolytic condensable group in the molecule represented by the above formula (I).

Specific examples of the above (A) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ
-Aminopropyltributoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyldibutoxysilane, N
-Β (aminoethyl) γ-aminopropylethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ
-Aminopropylethyldiisopropoxysilane, N-
β (aminoethyl) γ-aminopropylethyl dibutoxysilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane , Γ-aminopropylmethyldibutoxysilane, γ-
Aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, etc. Alternatively, two or more kinds can be used.

The composition for surface treatment of the present invention comprises the silane compound (A), the organometallic compound (C) and the compound (B).
(ABC) and the silane compound (A)
However, a reaction product (PABC) which is (co) hydrolyzed and condensed before or after the reaction between the organometallic compound (C) and the organic compound (B) is essentially contained. The organometallic compound (C) is an organometallic compound (C ₁ ) represented by the following general formula (II), or the organometallic compound (C ₁ ) and an organic compound represented by the following general formula (III) Organometallic compound (C ₁ + C) which is a mixture with silane compound (C ₂ )
₂ ) is used.

The organometallic compound (C ₁ ) is not particularly limited as long as it can be represented by the following general formula (II). R ⁷ _mm (OR ⁸ ) _n (II) (where M, R ⁷ , R ⁸ , m, and n have the same meaning as described above)

Specific examples include titanium alkoxides such as titanium tetraethoxide, titanium tetraisopropoxide and titanium tetrabutoxide; zirconium alkoxides such as zirconium tetraethoxide, zirconium tetraisopropoxide and zirconium tetrabutoxide; aluminum trioxide Ethoxide,
Aluminum alkoxides such as aluminum triisopropoxide and aluminum tributoxide may be mentioned.

The organic silane compound (C ₂ ) is not particularly limited as long as it can be represented by the following general formula (III). R ⁹ _o Si (OR ¹⁰ ) _p ... (III) (where R ⁹ , R ¹⁰ , o, and p have the same meaning as described above)

As specific examples, tetramethoxysilane,
Tetraethoxysilane, tetraisopropoxysilane,
Tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycid Xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
alkoxysilanes such as γ-chloropropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane; acyloxysilanes such as tetraacetoxysilane and methyltriacetoxysilane; and silanols such as trimethylsilanol.

The organometallic compound (C ₁ ) and the organometallic compound (C ₁ + C ₂ ) are collectively referred to as “organometallic compound (C)”. When one or two or more of these are hydrolyzed and condensed with the silane compound (A),
A co-hydrolysis condensate is formed.

The hydrolysis-condensation polymerization proceeds in the presence of the silane compound (A), the organometallic compound (C) and water.
When the hydrolyzable group in (A) or (C) is hydrolyzed and condensed, it is more advantageous to react in a solvent (D) described below as a composition for surface treatment. Silane compound (A)
Molar ratio of water and organometallic compound (C) to water (A + C)
/ W is preferably from 0.1 to 3. If it is less than 0.1, gelation tends to occur during polycondensation, and if it is more than 3, the reaction takes too much time, and unreacted compounds may remain. The reaction time is not particularly limited, but it is preferable that the hydrolysis-condensation polymerization reaction is completed. This is because, when a compound subjected to polycondensation in advance is used, the volume shrinkage is reduced when the hydrolytic polycondensation is sufficiently performed, so that the occurrence of cracks in the surface-treated film can be suppressed.

In this case, the organometallic compound (C) and / or
Alternatively, it is desired that the hydrolyzed condensate is used in an amount of about 1 to 200 mol%, preferably 1 to 100 mol%, based on the silane compound (A). If it is used more than 200%, the amine in the silane compound (A) may be used as a catalyst to form particles and rapidly gel.

The functional group having an aromatic ring or its hydrogenated ring used in the present invention and having reactivity with the amino group and / or Si (OR ⁴ ) group in the silane compound (A) is used as a molecule. The functional group of the compound (B) having two or more therein is an isocyanate group, an epoxy group, a carboxyl group, an oxazoline group, an alkoxysilyl group or the like,
These functional groups may be the same or different in the compound (B).

Further, from the viewpoint of water resistance, the functional group of the compound (B) preferably reacts with the amino group of the silane compound (A), and the functional group of the compound (B) also has an isocyanate group from the viewpoint of reactivity. And an epoxy group is preferred. Specific examples of compound (B) include tolylene diisocyanate, 1,4-
Isocyanates such as diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, trizine diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate; bisphenol A diglycidyl ether, resorcin diglycidyl ether, hydroquinone diglyridyl ether, o-phthalate Acid diglycidyl ester, tetraphthalic acid diglycidyl ester bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, and a compound represented by the following formula

[0029]

[Chemical 6]

When the compound has an aromatic ring, an epoxy group-containing compound such as a substituted derivative thereof may be used. Of these, one or two or more can be used, but bisphenol A diglycidyl ether is preferred from the viewpoint of versatility. As the compound (B), an oligomer may be used. Taking bisphenol A diglycidyl ether as an example, the oligomer can be represented by the following formula:

[0031]

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As the oligomer, those having n = 1 or more or a mixture of n = 0 and n = 1 or more can be used, but n = 1 represents 15% by weight in the compound (B).
And n = 0 is 85% by weight or more of the compound (B), more preferably n = 1 is 10% by weight or less in the compound (B) and n = 0 is 90% by weight or more of the compound (B) Is desirable. When n = 1 is more than 15% by weight in the compound (B), the gas barrier properties may decrease.

The amount of the compound (B) used is the amount of the compound (B) based on the amino group equivalent (X) of the silane compound (A).
Of the functional group equivalent (Y) is 0.1 to
1.0 is preferable, and more preferably 0.4 to 1.0,
More preferably, it is desirable to be 0.6-0.9. If the ratio of Y / X is less than 0.4, the humidity dependency of the gas barrier property becomes large, and the flexibility of the coating becomes insufficient, and if it is more than 1.0, the gas barrier property may decrease. The compound (B) contains an aromatic ring or its hydrogenated ring in the molecule, and this has an effect of extremely reducing the humidity dependence of the gas barrier property of the coating.

When the functional group of the compound (B) is an isocyanate group or an epoxy group, in order to prevent the hydrolysis reaction of the isocyanate group or the epoxy group or the reaction with the solvent (D), the amino group in the silane compound (A) is prevented. After reacting with the group, it is preferable to carry out cohydrolytic condensation of the silane compound (A) and the organometallic compound (B).

The solvent (D) used in the present invention includes:
The solvent is not particularly limited as long as the solvent dissolves the silane compound (A) and the compound (B), and specifically, methanol, ethanol, isopropanol, butanol,
Alcohols such as pentanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Aromatic hydrocarbons such as toluene, benzene and xylene;
Hydrocarbons such as hexane, heptane and octane; methyl acetate, ethyl acetate, propyl acetate,
Acetates such as butyl acetate; and others such as ethylphenol ether, propyl ether, and tetrahydrofuran. One or more of these can be used as a mixture. Of these, alcohols are preferably used. It is desirable to carry out the above-mentioned hydrolysis-condensation reaction using these solvents.

Various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, a defoaming agent and a thickener are added to the composition for surface treatment of the present invention as long as the effects of the present invention are not impaired. Agents can be added as needed.

As a substrate coated with the composition for surface treatment of the present invention, a resin molded product is used. The resin forming the molded article is not particularly limited, but is, for example, a polyolefin resin such as polyethylene and polypropylene; polyester such as polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and a copolymer thereof. Resin: polyoxymethylene, polyamide resin: polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, cellophane, polyimide, polyetherimide, polyphenylene sulfone, polysulfone, polyetherketone, ionomer resin , Fluoroplastics and other thermoplastic resins;
Melamine resin, polyurethane resin, epoxy resin, phenol resin, unsaturated polyester resin, alkyd resin,
Examples include thermosetting resins such as urea resin and silicon resin.

The shape of the molded article can be selected according to the intended use such as a film, a sheet, a bottle and the like. A thermoplastic film is particularly preferable because it is easy to process.

The method for coating the surface molding composition with the resin molding is not particularly limited, and a roll coating method, a dip coating method, a bar coating method, a nozzle coating method, or a combination thereof is employed. Before coating, the resin molded body may be subjected to a surface activation treatment such as a corona treatment or a known anchor treatment such as a urethane resin. After the surface treatment composition is coated on the resin molded body, a laminating treatment or other known treatment may be performed.

After coating, the coating is cured and dried, but the composition for surface treatment of the present invention is cured and dried even at room temperature. For faster curing and drying, heating at a temperature not higher than the heat resistant temperature of the resin molded body is recommended. The thickness of the film after drying is 0.001 to 20 μm, more preferably 0.01 to 1 μm.
0 μm is suitable. When the thickness is less than 0.001 μm, the coating is not uniform and pinholes are easily generated.
When the thickness is more than m, cracks are easily generated in the coating film, which is not preferable.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In addition, the evaluation method of the characteristic test was performed as follows. <Oxygen permeability> 20 according to JIS K 7126 B method
Measured in ° C. <Flexibility> After applying the surface treatment composition to 12 μm polyethylene terephthalate (hereinafter abbreviated as PET) to a predetermined thickness, the dried coating film was bent at 180 °,
も の indicates that no crack occurred, and X indicates that crack occurred. <Transparency> P coated in the same manner as in the flexibility evaluation test
The untreated ET film was visually compared with the untreated ET film, and those having no difference in transparency were evaluated as ○, and those having turbidity such as white turbidity were evaluated as ×.

Example 1 A flask equipped with a stirrer, a thermometer and a cooler was charged with γ-
50 g of aminopropyltriethoxysilane, 2 g of tetrabutoxytitanium, 25 g of bisphenol A diglycidyl ether, and 30 g of isopropyl alcohol were charged.
The mixture was heated to 70 ° C., reacted for 3 hours, cooled and added with 1.5 g of water and 100 g of isopropyl alcohol to obtain a composition for surface treatment for gas barrier. This composition was applied to a polyethylene terephthalate film having a thickness of 12 μm with a bar coater to a thickness of 2.0 μm, and dried at 80 ° C. for 1 minute.
The physical properties of the obtained surface-treated film were as follows: flexibility 、, transparency ○, and oxygen permeability at 0% Rh of 8.97 cc / m ^2.
Oxygen permeability at 24 hrs.atm and 85% Rh was 10.98 cc / m ² .24 hrs.atm.

Comparative Example 1 100 g of isopropyl alcohol and 1.5 g of water were added to 50 g of γ-aminopropyltriethoxysilane,
For 24 hours to obtain a composition 1 for comparative surface treatment. The composition 1 was applied to a PET film having a thickness of 12 μm to a thickness of 2.0 μm using a bar coater, and dried at 80 ° C. for 1 minute. Table 1 shows the physical properties of the obtained surface-treated film.

Comparative Examples 2-3 A surface-treated film was prepared in the same manner as in Comparative Example 1 except that various conditions were changed as shown in Table 1, and physical properties were tested. The results are shown in Table 1.

Comparative Example 4 A flask equipped with a stirrer, thermometer and cooler was charged with 50 g of tetraethoxysilane, 25 g of bisphenol A diglycidyl ether and 30 g of isopropyl alcohol, heated at 70 ° C. for 3 hours, cooled, and then cooled with water 2 2.0 g, isopropyl alcohol 200 g, concentrated hydrochloric acid 0.2 g,
The mixture was stirred at 21 ° C. for 24 hours to obtain composition 4 for comparative surface treatment. This composition was applied in the same manner as in Comparative Example 1 to obtain a surface-treated film. The results of the physical property tests are also shown in Table-2.

Comparative Example 5 A flask equipped with a stirrer, thermometer and cooler was charged with γ-
After adding 50 g of aminopropyltriethoxysilane, 60 g of bisphenol A diglycidyl ether and 30 g of isopropyl alcohol, heating at 70 ° C. for 3 hours and cooling,
1.5 g of water and 100 g of isopropyl alcohol were added to obtain Comparative Composition 5 for surface treatment. Comparative Example 1
And a surface-treated film was obtained. The results of the physical property tests are also shown in Table 1.

Comparative Example 6 A surface-treated film was prepared in the same manner as in Comparative Example 1 except that various conditions were changed as shown in Table 1, and physical properties were tested. The results are shown in Table 1.

Comparative Example 7 A flask equipped with a stirrer, a thermometer and a cooler was charged with γ-
Aminopropyltriethoxysilane (50 g), tetraethoxysilane (50 g), resorcinol diglycidyl ether (15 g) were charged, heated at 70 ° C. for 3 hours, cooled, and 1.5 g of water and 100 g of isopropyl alcohol were added. The solution gelled.

Comparative Example 8 A flask equipped with a stirrer, thermometer and cooler was charged with γ-
50 g of aminopropyltriethoxysilane and 10 g of diethylene glycol diglycidyl ether were charged,
After heating for 3 hours at 0 ° C. and cooling, 1.5 g of water and 100 g of isopropyl alcohol were added to obtain a comparative surface treatment composition 8. This composition was applied in the same manner as in Comparative Example 1 to obtain a surface-treated film. The results of the physical property tests are also shown in Table 1.

Comparative Example 9 A flask equipped with a stirrer, thermometer and cooler was charged with γ-
50 g of aminopropyltrimethoxysilane and 20 g of phenylglycidyl ether were charged, heated at 70 ° C. for 3 hours, cooled, and then cooled with 1.5 g of water and 100 g of isopropyl alcohol.
g was added to obtain Comparative Surface Treatment Composition 9. This composition was applied in the same manner as in Comparative Example 1 to obtain a surface-treated film.
The results of the physical property tests are also shown in Table 1.

[0051]

[Table 1]

The numbers in parentheses in Table 1 indicate weight. [Abbreviation] APTMS: γ-aminopropyltrimethoxysilane APTES: γ-aminopropyltriethoxysilane TBOT: Tetrabutoxytitanium NAEAPTMS: N-β (aminoethyl) γ-aminopropyltrimethoxysilane ES: Tetraethoxysilane BisADGE: Bisphenol A diglycidyl ether DEGDGE: diethylene glycol diglycidyl ether PhGE: phenyl glycidyl ether

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadahiro Yoneda 5-8 Nishimitabicho, Suita City, Osaka Pref.

Claims (4)

[Claims] (1) A silane compound (A) represented by the following general formula (I): Wherein A ¹ is an alkylene group, R ¹ is a hydrogen atom, a lower alkyl group, or (Where A ² represents a direct bond or an alkylene group, and R ⁵ , R ⁶
Represents a hydrogen atom or a lower alkyl group), R ² represents a hydrogen atom or a lower alkyl group, R ³ represents the same or different lower alkyl group, aryl group or unsaturated aliphatic residue, and R ⁴ represents a hydrogen atom , A lower alkyl group or an acyl group (provided that at least one of R ¹ , R ² , R ⁵ and R ⁶ is a hydrogen atom), w is any of 0, 1, and 2; (Where w + z = 3)] having an aromatic ring or a hydrogenated ring thereof, and having an amino group and / or Si (OR ⁴ ) in the silane compound (A).
A compound (B) having two or more functional groups having reactivity with a group in the molecule, and an organometallic compound (C ₁ ) represented by the following general formula (II): R ⁷ _mM (OR ⁸ ) _n . II) (wherein M is a metal element excluding Si, R ⁷ may be the same or different, and represents a hydrogen atom, a lower alkyl group, an aryl group or an unsaturated aliphatic residue, and R ⁸ is the same or different. A hydrogen atom, a lower alkyl group or an acyl group, m is 0 or a positive integer, n is an integer of 1 or more, and m + n matches the valence of the metal element M), or the organometallic compound (C ₁ ) and the following general formula (I
Organic silane compound represented by II) (C ₂₎ a mixture organometallic compound which is a (C ₁ + C ₂₎ [hereinafter, the organometallic compound (C ₁₎ and organometallic compound (C ₁ + C ₂₎ The "organometallic R ⁹ _o Si (OR ¹⁰ ) _p ... (III) (wherein R ⁹ may be the same or different and is a hydrogen atom, a lower alkyl group, an aryl group, or an unsaturated aliphatic group) Represents a residue, R ¹⁰ may be the same or different and represents a hydrogen atom, a lower alkyl group or an acyl group, o is 0 or a positive integer, p is an integer of 1 or more, and o + p is S
(2) The silane compound (A) is reacted with the organometallic compound (C) and the organic compound (B) before or after the reaction. (Co) hydrolysis-condensed reaction product (PABC),
(1) A composition for surface treatment for a gas barrier, comprising at least one reactive compound selected from the group consisting of (1) and (2), and a solvent (D). 2. The gas barrier surface treatment composition according to claim 1, wherein the compound (B) is an organic compound having two or more epoxy groups in a molecule. 3. The surface treatment composition according to claim 1, wherein the compound (B) is an organic compound having two or more isocyanate groups in a molecule. 4. A surface-treated resin molded article obtained by treating at least one surface of the resin molded article with the composition for surface treatment for gas barrier according to claim 1.